Condensation product of isatin-alpha-anilide and substituted anthrones and process of producing same



Patented Mar. 28, 1933 UNITED STATES PATENT? OFFICE KARL ZAHN, OFFRANKFORT-ON-THE-MAIN-HOCHST, GERMANY, ASSIG-NOR TO GENERAL ANILINEWORKS, INC., 015 NEW YORK, N. Y., A CORPORATION OF DELA- WARECONDNNSATION IRODUCT OF ISATIN-a-ANILIDE AND SUBSTITUTED ANTI-IRONES ANDPROCESS OF PRODUCING SAME No Drawing. Application filed June 4, 1930,Serial No.459,260, and. in Germany July 16, 1929.

My present invention relates to condensation products ofisatin-alpha-anilide and substituted anthrones and process of producingsame.

I have found that the reduction products of acetylated1.-dihydroxy-anthraquinones, obtainable for instance by the reduction of1A diacetyloxy-anthraquinones in an acetic acid suspension withhydrosulfite and having the general formula:

wherein the nucleus N may contain substituents and R represents anacetyl group, can be etherified in one hydroxyl group, the acetyl groupbeing split off by treating the 'compounds for a short time with analiphatic alcohol in the presence of amineral acid as, for instance,hydrochloric acid or sulfuric acid.

This reaction occurs with a surprising facility hitherto not observedwith hydroxy derivatives of the anthrone series.

Instead of the above mentioned reductionproducts of acetylated1.4-di-hydroxy-anithraquinones there also may be used as startingmaterials the corresponding lAt-dihydroxyanthrones obtainable bysaponification of the said acetylated products.

I have further found that the others thus obtained of the followinggeneral formula 2 with an lSZEtlIl-oc-dGllVLtlVB as, for example,

an isatin-a-anilide whereby valuable greenish blue to green vatdyestuffs are obtained. This reaction could'not be foreseen, as itwasfound outthat not all of the a-hydroxyanthrones can be condensed withisatinfl-de- Homolka) rivatives. Thus, for example, the reductionproducts of l-acetoxy-anthraquinone and the l.8 diacetoxy-anthraquinoneare not condensable with isatin-a-anilide.

- Hitherto it was only known that the reduction'produot of1-hydroxyanthraquinohe can be condensed with isatin-a-derivatives so asto form vat dy'estufi's (see U. S. .Patent Specification No. 1,025,174dated May 7th, 1912 in the name of Robert Welde and Benno I EVE R om n(I) 0 \do 7 I wherein the nuclei N may contain substituents and Zrepresents an alkyl group.

The following examples illustrate the ill-.-

vention, the parts being by weight: 1

(1) 54 parts of l-hydroxy-t acetoxy-lO- anthrone of the formula:

H H on I O COCHa (obtainable by reducing diacetylquinizarine in anacetic acid suspension with sodiumhydrosulfite) are heated to boiling ina reflux apparatus with 500 parts of methanol and 100 parts ofconcentrated hydrochloric acid. The starting material. gradually passesinto solution with a yellowish-brown coloration and after a short timethe separation of the reaction product begins inthe formof yellowneedles. time and after cooling, the entire mixture is filtered bysuction. 'When recrystallizing the product from glacial acetic acid, thepure Boiling is continued for. some 7 I monomethylether of1.4-dihydroXy-anthrone is obtained, melting at 156 C. to 157 C. andhaving'the formula OOH: I

24 parts of the ether thus obtained are dissolved in 120 parts ofpyridine and heated on the, steam-bath with 28parts of isatina-ani'lide.The formation of dyestufi" soon sets'in and is complete after a fewhours. After cooling,'the dyestufi is filtered by suction, washedtwithalcohol and water and dried. An indigolike'dark-blue powder is -obtainedwhich is soluble in concentrated sulfuric acid to a green solution,insoluble in water and in low boiling solvents and soluble in hotnitrobenzene to agreenish-blue solution. "With" alkaline ,hydrosulfitethe dye- ;istllfi gives an orange colored vat with which cotton and woolare dyed greenish blue tints. The dyestufi probably has the followingconstitution: r I i n H 00m I (2) By substituting for the quantity ofmethanol employed inExample (1), 300 parts of ethyl alcohol andotherwise proceeding as indicated in Example (1) the correspondingmonoethylether of the lAc-dihy'droxy-anthrone is obtained in the form ofyellow needles melting at 145 C.14:6 C. The ether probably'has thefollowing constitution'.:'

H. E (X32115 I O OH If 25 parts of this ether are heatedto boiling with30jparts of 5-chlorizatin-a -parachloranilide in 200 parts of aceticanhydride,

a dyestuff is obtained which as regards its qualities is very similar tothe product of Example (1) 7 The dyestulf probably has the followingconstitution? (3) 30 parts of 5.8 dichloroJ-hydroxyiaoetoxy-lO-anthroneof the formula:

31 parts of this dichlorether are condensed in the usual manner with 25parts of isatin-a-anilide in pyridine. A dyestuif is obtained whichproduces on the fiber intense green tints of very good fastnessproperties.

The dyestuff probably has the following con- It dissolves inconcentrated sulfuricQacid to 7 an olive green and in hot nitrobenzeneto a bluishegreen SOlUtIOIL' I claim; 7 I l. The process which comprisestreating a compound of the following general formula:

X 0 O.R

wherein R stands for hydrogen or an acetyl group and X for hydrogen orchlorine with an aliphatic alcohol in the presence of a I I I I 01 c) Hr mineral acid and causing the products, thus 7 obtained, which have thefollowing general formula Y X 352 oz wherein X stands for hydrogen orchlorine j and Z' for alkyl to condense with an isatina-anilide.

2. The process which comprises treating a compound of the followinggeneral formula:

X 0 O.R

wherein R stands for an acetyl group and X for hydrogen or chlorine withan aliphatic alcohol in the presence of a mineral acid and causing theproducts, thus obtained, which have the following general formula:

X 0 OH wherein X stands for hydrogen or chlorine and Z for methyl orethyl to condense with an isatin-a-anilide.

3. The process which comprises treating a compound of the followinggeneral formula:

X 0 O.COCH:

wherein X stands for hydrogen or chlorine with methyl alcohol in thepresence of a mineral acid and causing the products, thus obtained,which have the following general formula:

anthrone, thus obtained, to condense with is'atin-a-anilide.

5. As new products, compounds of the following general formula:

wherein X stands for hydrogen or chlorine and Z for methyl or ethylbeing vat dyestufis of very good fastness properties.

6. As new products, compounds of the following general formula:

wherein X standsfor hydrogen or chlorine being vat dyestuif of very goodfastness properties.

7. -As a new product, the compound of the following formula:

CI H H 0.0Ha

| i I V r O NH 7 1 i ('i T 0/0 being a vat dyestufi' which dissolves inconcentrated sulfuric acid to an olive green solution and in hotnitrobenzene to a bluish-green solution and dyes the fiber intense greentints of very good fastness properties.

8. As a new product, the compound of the following formula:

H H OOHa.

l I on;

a, a. loo/O being a vat dyestufi' which is soluble inconcentratedsulfuric acid to a green solution and in hot nitrobenzene to agreenish-blue solution and gives an orange colored vat from which cottonand wool are dyed greenish blue tints.

9. As a new product, the compound of the following formula:

H H 00in,

being a vat dyestufl' which is soluble in concentrated sulfurlc acid toa green solution and in hot nitrobenzene to a greenish-blue solution andgives an orange colored vat from which cotton and wool are dyedgreenish-blue tints.

In testimony whereof, I aflix my signature.

KARL ZAHN.

